Straight-chain alkylated alpha and beta naphthols



3,548,011 STRAIGHT-CHAIN ALKYLATED ALPHA AND BETA NAPHTHOLS Harry J. Andress, Jr., Pitman, and Paul Y. C. Gee, Woodbury, N.J., assignors to Mobil Oil Corporation, a corporation of New York No Drawing. Original application Nov. 27, 1964, Ser. No. 414,426. Divided and this application Nov. 27, 1967, Ser. No. 685,962

Int. Cl. C07c 39/14 US. Cl. 260-624 3 Claims ABSTRACT OF THE DISCLOSURE Straight-chain alkylated alpha and beta naphthols having from about 8 to about 30 carbon atoms penalkyl chain are employed as stabilizers in liquid hydrocarbon compositions.

CROSS-REFERENCES TO THE RELATED APPLICATION Application Serial No. 414,426, filed Nov. 27, 1964 now abandoned (parent application).

BACKGROUND OF THE INVENTION Field of the invention Description of the prior art It is well known that liquid hydrocarbons in the form of fuel oils are prone to form sludge or sediment, during periods of prolonged storage. Such sludge or sediment have an adverse effect on burner operation by reason of their tendency to clog screens and nozzles. In addition to sediment and sludge which are formed during storage, most fuel oils contain other impurities such as rust, dirt and entrained water. Such sediment sludge and other impurities tend to settle out on equipment. parts such as nozzles, screens, filters and the like, thereby causing clogging and failure of equipment. Furthermore, another undesirable characteristic of petroleum distillate fuel oils is their tendency to form objectionable emulsrons.

A factor incident to the sludge and handling of distillate fuels, is the breathing of storage vessels. This results in the accumulation of considerable amounts of water in the tanks and presents the problem of rusting. Consequently, when the fuel is removed for transportation, sufficient water may be carried along to cause rusting of ferrous metal surfaces in pipe lines, tankers and the like.

Heretofore, in the case of fuel oils, it has been the practice to overcome the aforementioned ditficulties through the use of a separate additive for each purpose, i.e., with a sediment inhibitor, an anti-screen clogging agent, an antirust agent and an emulsion inhibitor. The use of several additives, however, gives rise to problems of additive compatability, thus restricting the choice of additive combinations. In addition, of course, the use of a plurality of additives unduly increases the cost of the fuel. It is, therefore, highly desirable from a com- United States Patent ice mercial standpoint to overcome the aforementioned difficulties through the use of a single additive agent, which is effective against sediment formation, screen and nozzle clogging, rusting of ferrous metal surfaces and emulsification.

SUMMARY OF THE INVENTION It has now been found that all of the aforementioned difliculties, viz, sedimentation, screen clogging, rusting and emulsification, can be overcome by the use of a single fuel oil addition agent. In this respect, it has now been found that liquid hydrocarbons, and particularly petroleum distillate fuel oils, containing minor amounts of certain straight-chain alkylated alpha and beta naphthols, are effectively inhibited, simultaneously, against all of the aforementioned difficulties.

The present invention, in general, provides improved liquid hydrocarbons, preferably in the form of nonlubricating petroleum distillate hydrocarbons containing from about 1 to about 200, and preferably from about 5 to about 50, pounds per 1,000 barrels of liquid hydrocarbon of a straight-chain alkylated alpha or beta naphthol having from about 8 to about 30 carbon atoms per alkyl chain.

The addition agents contemplated herein are, in general, produced by catalytically reacting an alpha olefin or an alkyl halide having from about 8 to about 30 carbon atoms per alkyl chain with either alpha or beta naphthols to produce a corresponding reaction product comprising a straight-chain alkylated alpha or beta naphthol having from about 8 to about 30 carbon atoms per alkyl chain. The reaction is carried out, generally, at a temperature from about C. to about 250 C. When alpha olefins are reacted with either alpha or beta naphthols, temperatures from about 75 C. to about 100 C. are preferably employed, and temperatures from about C. to about C. are most desirable for this reaction. When alkyl halides are reacted with either alpha or beta naphthols, temperatures from about C. to about 250 C. are preferred. The catalyst employed in the reaction comprises an alkylation catalyst, preferably of the Friedel-Crafts type, as typified, for example, by boron trifiuoride, or zinc chloride. Following reaction between the aforementioned components, the reaction product is washed with hot water until neutral washings are obtained. The final product, an alkylated alpha or beta naphthol, is obtainable by topping under reduced pressure at temperatures from about 200 C. to about 250 C., and preferably from about 220 C. to about 240 C., as more fully hereinafter described.

The liquid hydrocarbons improved in accordance with the present invention are those boiling from about 75 C. to about 750 C. Of particular significance is the treatment of petroleum distillate fuel oils having an initial boiling point from about 75 F. to about F., and an end boiling point from about 250 F. to about 750 F. It should be noted, in this respect, that the term distillate fuel oils is not intended to be restricted to straight-run distillate fractions. The distillate fuel oils can be straightrun distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillate fuel oils, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well known commercial methods, such as acid or caustic treatment, hydrogenation, solvent refining, clay treatment and the like The distillate fuel oils are characterized by their relatively low viscosity, pour point and the like. The principa'l property which characterizes: the contemplated hydrocarbons, however, is the distillation range. As hereinbefore mentioned, this range will lie betwen about 75 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.

Particularly contemplated among the fuel oils are Nos. 1, 2 and 3 fuel oils used in heating and as Diesel fuel oils, gasoline and the jet combustion fuels. The domestic fuel oils generally conform to the specifications set forth in ASTM Specifications D396-48T. Specifications for Diesel fuels are defined in ASTM Specifications D975-48T. Typical jet fuels are defined in Military Specification MIIrF-5624B- DESCRIPTION OF SPECIFIC EMBODIMENTS The following examples will serve to illustrate the preparation of the straight-chain alkylated alpha and beta naphthols of the present invention and to demonstrate the effectiveness thereof in rendering the afore mentioned liquid hydrocarbons, and particularly petroleum hydrcarbon distillate fuels, thermally stable. It will be understood that it is not intended that the'invention be limited to the particular compositions shown, or to the operations or manipulations involved. Various modifications of these additives, as previously described, can be employed and will be readily apparent to those skilled in the art.

EXAMPLE 1 A mixture of 295 grams (2.13 mols) of a C C alpha olefin fraction comprising, by weight, 1% l-octene, 25% l-nonene, 53% l-decene and 21% l-undecene, and having an average molecular weight of 139; 102 grams (0.71 mol) alpha naphthol and 25 grams boron trifluoride ethyl etherate, was stirred for a period of about 8 hours at 95 C. The resulting reactionmixture was then washed with hot distilled water until the washings were neutral to litmus paper. The final product, a mixture of tri-alkylated alpha naphthols, was recovered by topping under reduced pressure at 240 C.

EXAMPLE 2 A mixture of 1112 grams (8.0 mols) of a C C alpha olefin fraction (having the composition described in Example 1), 288 grams (2.0 mols) alpha naphthol and 42 grams boron trifiuoride ethyl etherate, was stirred for a period. of about 1 2 hours at 95 C. The resulting reaction mixture was then washed with hot distilled water until the washings were neutral to litmus paper. The final product, a mixture of tetra-alkylat'ed alpha naphthols, was recovered by topping under reduced pressure at 230 C.

EXAMPLE 3 A mixture of 102 gram (0.71 mol) alpha naphthol; 68-6 grams (2.84 mols) of a C -C alpha olefin fraction comprising, by weight, 12% l-pentadecene, 22% 1- hexadecene, 20% l-heptadecene, 19% l-ootadecene, 17% l-nonadecene and l-eicosene, and having an average molecular weight of 242, and 35 grams boron trifluoride ethyl etherate, was stirred for a period of about 11 hours at 95 C. The resulting reaction mixture was then washed with hot distilled water until the washings were neutral to litmus paper. The final product, a mixture of tetra C C alkylated alpha naphthols, was recovered by topping under reduced pressure at 215 C.

EXAMPLE 4 A mixture of 400' grams (1.36 mols) of 12% chlorowax (a chlorinated parafiin wax containing 4 atomic proportions of chlorine and having a chlorine content of were neutral to litmus paper. The final product, a wax alpha naphthol (4-12), was recovered by topping under reduced pressure at 245 C.

EXAMPLE 5 A mixture of 120 grams (0.83 mol) beta naphthol, 767 grams (3.33 mols) comprising, by weight, 6% 1- dodecene, 14% l-tetradecene, 42% l-hexadecene, 33% l-octadecene, and 5% l-e-icosene, and having an average molecular weight of about 230, and 35 grams boron trifiuoride ethyl etherate was stirred for a period of about 10 hours at C. The resulting reaction mixture was then washed with hot distilled water until the washings wereneutral to litmus paper. The final product, a mixture of tetra-alkylated beta naphthols, was recovered by topping under reduced pressure at 225 C.

EXAMPLE 6 A mixture of 86.4 grams (0.6 mol) alpha naphthol, 403.2 grams (2.4 mols) of l-dodecene, and 25 grams of boron trifluoride ethyl etherate was stirred for about 14 hours at 9095 C. The resulting reaction mixture was then washed with hot distilled water until the washings were neutral to litmus paper. The final product, a tetradodecyl alpha naphthol, as recovered by topping under reduced pressure at 320 C.

EXAMPLE 7 A mixture of 86.4 grams (0.6 mol) beta naphthol, 403.2 grams (2.4 mols) of l-dodecene, and 25 grams of boron trifluoride ethyl etherate was stirred for about 14 hours at 90-95 C. The resulting reaction mixture was then washed-with hot distilled water until the washings were neutral tolitmus paper. The final product, a tetradodecyl beta. naphthol, was recovered by topping under reduced pressure at 220 C.

Each of the products of the foregoing examples was subjected to tests under the conditions of a test method used for determining the thermal stability characteristics of aviation turbine fuels. This method was developed by the Coordination Research Counsel as published in CRC Report Investigation of Thermal Stability of Aviation Turbine Fuels with CFR Fuel Coker. (CRC Project CFA-2-54) July 1957. This method is set forth in detail in Appendix XV of the ASTM Standards of Petroleum Products and Lubricants November 1957, commencing on page 1059. This method provides a means for measuring the high temperature stability of aviation turbine fuels, using an apparatus known as CFR Fuel Coker, which subjects the test fuel to temperatures and conditions similar to those occurring in some aviation turbine engines.

Fuel is pumped, at a rate of about 6 pounds per hour, through a preheater section which simiulates the hot fuel line section of the engine as typfied by an engine fueloil cooler. It then passes through a heated filter section which represents the nozzle area or small fuel passages of the hot section of the engine where fuel degredation products may become trapped. A precision sintered stainless steel filter in the heated filter section traps fuel degredation products formed during the test. The extent of the build-up is noted as an increased pressure drop across the test filter and, in combination with the deposit condition of the preheater, is used as an assessment of the fuels high-temperature stability. In the testing described herein, the filter temperature was 600 F. to 650 F. and the preheater tube temperature was from 500 to 550 F. In each run, the test was continued until there was a pressure drop of 25 inches of mercury across the filter or until a time interval of 300 minutes had elapsed, whichever occurred first. In order to be satisfactory in the test, a fuel should show little or no pressure drop across the filter at the end of the 300 minutes. The preheater deposits in the tests are evaluated according to a code rating varying from 0 to 8, as shown in the following table, in which a rating lower than Code 3 is desirable for an effective stable aviation turbine fuel. I

The base hydrocarbon jet combustion fuel, as exemplifying the liquid hydrocarbon compositions and the petroleum distillate fuel oils of the present invention, employed in connection with the data disclosed in the table, was a straight-run petroleum fraction comprising 100% We claim:

1. A compound prepared by: reacting alpha olefinic hydrocarbon having from about 8 to about 30 carbon atoms with a compound selected from the group consisting of alpha and beta naphthols at a temperature from v n o o isoparaflins, bOlllIlg within the range of approximately 5 2 9 3 i 250 the g? of a I n U 330 F. to 400 F. Portlons of this base fuel, uninhibited, :3 i i is ii gfg sg g if g were subjected to the Fuel Coker Test, then, other porp g p c n g tio of the b so fuel were blended with the reaction stra1ght-cha1n tri and tetra alkylated alpha and beta n a naphthols having from about 8 to about 30 carbon atoms products of the foregoing examples, and each blend so per alkyl chain obtained was subjected to the Fuel Coker Test. Pertinent 2. A Compound prepared in accordance with Claim 1 Plended data and test results are Set forth In the follow wherein said reaction is carried out in the presence of a mg table. boron trifluoride-containing catalyst.

TABLE C 1 Filter one. p ugging lbsj Filter Preheater prmsure 1,000 mp., temp, drop Run N o. Inhibitor bbls. F. F. inches H'g Preheater deposits at 300 min., rating 1 Uninhibited Jet Fuel 0 650 550 0.0 39% Code 2, 8% Code 4, Code 7, 15% Code 3, 8% Code 5, 15% Code 8. 2 Fuel plus alkylated naphthols of Example 1..- 650 550 0. 0 100% Code 2. 3 Fuel plus alyklated naphthols of Example 2.-. 20 650 550 0. 0 Do. 4-- Fuel plus alkylated naphthols of Example 4... 20 650 550 0.0 Do. 5-. Uninhibited Jet Fuel 0 600 500 0.0 55% Code 1, Code 5, 15% Code 7. 6 Fuel plus alkylated naphthols of Example 3 20 600 500 0.0 100% Code 2. 7 Fuel plus alkylated naphthols of Example 5 20 600 500 0. 0 100% Code 2. 8. Fuel plus alkylated naphthols of Example 6"- 20 600 500 0. 0 Do. 9 Fuel plus alkylated naphthols of Example 7..- 20 600 500 0. 0 Do.

NOTE: Code 1, drilling of preheater. Code 2, slight discoloration. Code 3, light tan. Code 4, medium tan. Code 5, light brown. Code 6, medium brown. Code 7, dark brown. Code 8, black. As is apparent from the foregoing data in the table 3. A compound prepared in accordance with claim 1 the uninhibited jet fuel (Runs 1 and 5) had unsatisfactory ratings (ranging to a large extent from Code 3 to Code 8), with respect to preheater deposits. The marked improvement that results from the practice of this invention by employing the aforementioned straightchain alkylated alpha and beta naphthols having from about 8 to about 30 carbon atoms per alkyl chain, as fuel additives, is evidenced from the data set forth for Runs 2, 3, 4, 6, 7, 8, and 9. As shown, the fuel compositions containing the aforementioned straight-chain alkylated naphthols passes the requirements of the test, i.e. Code 2, and with no pressure drop across the filter after a period of about 300 minutes.

While preferred embodiments of the additives and fuel compositions of the present invention, and the process for their preparatioin, have been described for purposes of illustration, it should be understood that various modifications and adaptations thereof, which will be obvious to those skilled in the art, may be made without departing from the spirit of the invention.

wherein said reaction is carried out in the presence of a zinc chloride-containing catalyst.

References Cited UNITED STATES PATENTS 2,073,996 3/ 1937 Raiziss et a1. 260624 2,090,938 8/1937 Conrad 260624 2,091,438 8/1937 Olin 260624 2,110,077 3/1938 Brubaker 260624 FOREIGN PATENTS 906,219 9/ 1962 Great Britain 260624 129,203 10/ 1959 Russia 260624C BERNARD HELFIN, Primary Examiner W. B. LONE, Assistant Examiner US. Cl. X.R. 445 6 23 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,5 +8,0ll Dated December 15. 1970 Inventofls) Harrv J. Andress Jr. and Paul Y.C. Gee

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 26, for "320C. read --22oc.--.

Column line 52, for "sirriulates" read --simulates-- Column t, line 53, for "typfied" read -typified--.

mam mu SEALED N9 1971 $1.11 M Atheist:

mm M Fletch, 1'' m E- Wm, JR A ni Officer Mundane:- of Patents 

